Process for transformation of petroleum hydrocarbons into gasoline



u. s. JENKINS LMM PROCESS FOR TRANSFORMATION OF PETROLEUM HYDROCARBONS INTO GASOLINE Filed Nov. 16, 1928 Patented Jul'y 14, 1931 UNITED lSTATES PATENT .ori-ICE i 'ULYSSES S. JENKINS, OF CHICAGO, ILLINOIS, ASSIGNOR TO `JENKINS PETROLEUM PROCESS COMPANY, F CHICAGO, ILLINOIS, A CORPORATION OF WISCONSIN PROCESS FOR TRANSFORMATION OF PETROLEUM HYDROCARBONS AINTO GASOLIN Application led November 16, 1928. Serial No. 319,923.

The present invention is a` continuation in part of my application Serial No. 723,144-, filed June 30, 1924, entitled Means and methods of distilling, l

My inventionfrelates to certain improvements in the treatment of petroleum hydrocarbons, and particularly to a process for the continuous transformation of by-product-residual hydrocarbons or their naturally occurring equivalents into gasoline and coallike complexes.

'In the ordinary distillation of petroleum and the subsequent conversion of intermediates` under relatively high temperatures and pressures Jinto gasoline, there is produced along with such desired objective, varying quantities of residual fuel oil and/or coke and Waste permanent gas; dependent upon the temperatures and pressures imposed, and the general severity of cracking methods employed.

The production offuel oil and coke is open not only to the commercial objection of their relatively low market value, b t the formation of the latter is eected at a temperature prejudicial to the longevity of the apparatus commonly-employed, and in the case of its formation under pressure, the process may assume a dangerous character as Well.

Various methods have been suggested to prevent the production of fuel oil as an end- .product of cracked, gasoline production; a

known method being the coking at atmospheric pressure of the fuel oil intermediately produced, with formation of an easily convertible distillate as the major, and a hard still coke as the ininor secondary reaction products. Suc-h process, however, requires the handling of comparatively large quantities of fuel oil in batch stills, involving a relatively high operative, maintenance and investment cost. n

Another described process Vconcerns the continuous or intermittent production of a pitchy carbon, Wet with a content of liquid oil residuum; ,but such process is likewise open to the commercialobjection of handling large quantities of material of-a voluminousA nature, is further uneconomic in character because of the liquid o il content receiving the o into gasoline Without formation of fuel oil and coke end-products.

Another genera-l object of the invention is to effect the continuous transformation, un-l der such previously described conditions, of a petroleum hydrocarbon into gasoline as the major, and a dry coal-like complex as the minor reaction products.

An additional general object of the invention is to effect such above described -transformation by thecontinuo'us produc-. tion of the gasoline objective under crack ing conditions of heat and pressure best s uited for quality desired, from easily convert.. ible distillates intermediately obtained, while concurrently effecting the contin'uous formation of a dry coal-like complex as a final end-product of the transformation reaction. ,y

A further object of the invention is to cause such, continuous transformation into lgasoline in the manner, and from the interme diate distillates previously described, concurrently with the continuous formation of a dry coal-like complex end-product; effecting the continuous production of such distillates, by their progressive volatiliza-tion from primary and intermediate residuals respective` ly, upon which pressures are alternately imposed and released, while such residuals arl` 1- continuously maintained at temperatures re spectively best suitedfor accomplishing the desired degree of vaporization.

A correlative object of the inventionis to effect such continuous transformationn into gasoline in the manner, andl from intermediates previously described, by effecting their continuous production at temperatures' and under pressures as to form' distillates of a chemical structure best suited for subsequent maximum gasoline conversion', concurrently.. m

and concordantly with the continuous formation of a final dry coal-like end-product.

Another object of the invention is to effect such continuous transformationinto gasoline in the manner, and from the intermediates previously described ;Wherein such distillates are initially obtained by continuously subjecting a primary residual, ornaturally occurring equivalent, to a temperature and under a pressure that with subsequent reduction of the latter in a non-extraneously heated zone, will continuously produce a predominant yield of vaporized distillate of an easily convertible nature, and a liquid residual composed of free carbon suspended in a complex polymeride matrix.

A further object of the invention is to effect such continuous transformation into gasoline in the manner and from the intermediates previously described, wherein such distillates are progressively obtained by subjecting the previously mentioned intermediate liquid residual to a temperature and under a pressure, that with subsequent substantial reduction of the latter in a non-extraneously heated zone, WilL produce a predominant yield of vaporized distillate of an easily convertible nature, and a liquid residual at the temperature involved, composed of free carbon suspended in a highly complex polymeride matrix.

An additional object of the invention is to effect such continuous transformation into gasoline in the manner, and from the distillates previously described; wherein such distillates are initially and progressively vaporized from primary and intermediate residuals, containing asuticient quantity of suspended hydrated lime or other agent producing a like effect, as to form an adsorptive binder for the concurrently produced carbon and complex polymeride matrix.

A correlative object of the invention is to effect such continuous transformation into gasoline in the manner, and from the intermediates previously described; wherein such distillates are initially and progressively vaporized with a final degree of vaporization controlled so that the residual complex of adsorptive binder, free carbon and polymerides of high molecular Weight remains in substantially a liquid condition in the final zone of evaporation, and assumes a dry coal-like structure upon solidification wit-hout the system.

A further correlative object of the invention is-to effect such continuous transformation into gasoline in the manner, and from the intermediates previously described; wherein such distillates are finally evaporated in the prese-nce of an adsorptive binder -as to produce a dry coal-like end-product without the system with a volatile carbon and ash content corresponding to known existing coal.

Another object of the invention is to effect such previously described continuous transformation into gasoline and dry coal-like complexes; wherein such a coal-like residue retains a suiicient quantity of hydrogen to be readily re-converted into petroleum hyd rocarbons in the presence of additional hydrogen under conditions of heat' and pressure of a process known in the arts.

An incidental object of the invention is to effect such previously described continuous transformation into gasoline and dry coallike complexes,` wherein the initially producedintermediate distillate is continuously converted into Ygasoline under Vcracking conditions of heat and pressure bestsuited for quality desired, and selective portions of the progressively produced intermediate distillate are converted into lubricating stocks and/or paraiiin wax, and the less preferred distillates from such treatment continuously converted into gasoline in a manner previously described.

A further incidental object of the inventio'n is to etl'ect the continuous transformation of petroleum hydrocarbon into gasoline and coal-like complexes; wherein the previously described intermediate distillate is initially evaporated from a primary residual (or a naturally occurring equivalent) that has been previously subjected to such conditions ot' heat and pressure as to suffer some degradation.

An additional incidental object of the invention is to cause such continuousl transformation of a petroleum hydrocarbon into gasoline and dry coal-like complexes; wherein the previously mentioned intermediate distillate is initially evaporated from a primary residual continuously released from a still of freely connecting channels dominated by a bulk supply, maintained at a temperature and under a pressure best suited for maximum gasoline production; Awhile concurrently effecting continuous charging of raw material and adsorptive binder thereto, continuously releasing preferred gasoline fractions therefrom, and simultaneously maintaining a positive liquid cyclic circulation therein.

Another incidental object of the invention is to cause such continuous transformation of a petroleum hydrocarbon into gasoline and dry coal-like complexes; wherein the previously mentioned intermediate distillate is initially evaporated from a primary residual, continuously released from a still of the type described; and to which such condensed intermediate distillate, together with similar heavier distillate progressively obtained, is returned for further transformation.

In order that the invention may be better understood, reference Will be made tothe accompanying diagrammatic drawing, Fig. l. i

1, represents a cracking still well known in the art, from which a high yield of gasoline A may be obtained concurrently with the production of a somewhat degraded primary residual, preeminently suited for the transformation previously described. Such still comprises a horizontal cylindrical drum 2, superimposed over connecting front and rear sluiceways 3 and 4, themselves suprajacent to front and rear cross drums 5 and 6, which are connected by the inclined tube bank 7, so as to form a series of freely connecting channels dominated by the bulk supply Idrum 2.

The still 1 is further provided with liquid level gauge 8, safety, valves 9 and4 10, and prpellerll, mounted in rear sluiceway 4, on shaft 12, extending through stuiiing box 13 and driven by motor 14; The still is erected over furnace 15 which may be heated by any desired fuel, burners 16 and 16' showing a typical arrangement for gas and fuel oil respectively; the waste heat gases from the furnace 15 escaping to the atmosphere through the underground flue 17 and stack 18.

The vapor line 19 leads to the reflux tower 2,0 which is further unrestrictedly 'connected to the still 1 by reflux line 21. YVhen cracking conditions have been established in still 1 with accompanying production of gasoline through vapor line 19, secondary continuous chargin o the system from blending supply ktan 22, is effected by high pressure pump 23, through suction line 24, past control valve 24', discharging through line-25,

y past check valve 25', to top of reflux tower 20; a pre-.determined quantity of adsorptive binder being simultaneously introduced tol the system through line 25 from a small 'mixling tank not shown inthe drawing. At the same time a substantial quantity of somewhat degraded stock from the simultanelouslypositively circulated still contents is continuously released through lines 26 and 26 as controlled by stop valves 27, 27', 27 and automatic and/or hand controlled relief valve 28, to low pressure vapor separator 29;

from which the therein separated recyclef` stock vapor escapes through line 30 to be utilized in a manner subsequently to be described. Emergency relief of the still contents is afforded through line 31 as controlled by stop valve 31', to emergency cooler 32.

The initially separated residuum in the low pressure vapor separator 29, (or a` naturally occurring product of similar specification) iows past stop valve 33, and through lines 34 and 26, past stop valve 35 to the surge tank 36, provided with try-cocks 37,37', 37". The hot reduced residuum is next pumped by pressure pump 38, through line 39 past control valve .39' (provision being made for the use of a controlled amount of superheated steam, introduced through line 40 as regulated by valve 40')A to the secondary heating coil 41, located in furnace 42, which may be heated by any desired mea-ns; the burners 43 and 43' Ishowing a typical ar-` rangement for gas andfuel oil respectively, with the waste heat furnace gases passing to the atmosphere through stack 44; or such coil may be heated by the instrumentality of the primary furnace 15, if desired.

The above described residuum is continuou'sly maintained in coil 41, (which may be replaced by a plurality of manifolded tubular sections, or a still comprising a series of freely connecting tubular channels dominated by a bulk supply) at a temperature, and under a pressure for a time inhibitive of substantial cracking; but of sufficiently intense conditionsthat upon release of pressure, or further reduction thereof, in the secondary low pressure Vapor separator 47, to which the residuum from coil 41 is continuously discharged through line 45, as regulated by the-automatic and/or hand controlled pressure release valve 46; so that sufficient separation of vapor will occur in such low pressure vapor separator, that the resultantl residuum formed therein, will solidify without the system into the previously described coal-like complex.

The vaporized secondary recycle stock released in low pressure 'vaporizer 47, flows through line 48, to `exchanger shell 49, andV thence through condensing coil .50 located in condenser box50', to flow tank 51, upon which a varying absolute pressure may be' maintained; thus controlling the quality and percentages of recycle vapor and liquid residuum separated in the low pressure vapor separator 47. Such varying absolute pressure may be imposed on the system through line 52, as controlled by valve 52 by means Well known in the art; further control of the tem- 1 further conversion, by proper adjustment of Valves 55 and 55'; or such condensate may be pumped through line 56 for lubricating oil recovery, or other treatment as may be desired, by a different setting of the valves in question. r

The hot liquid mixture of free carbon and adsorptive binder suspended in the highly complex polymeride matrix, separated in the low pressure vapori'zer 47 may be conductedtherefrom by line 57 to moulds or other containers, where it shortly assumes the dry coallike structure previously described; or through the agency of the pump 58 and control valves 59, 59', 59",' it may be pumped in a liquid condition through a properly insulated line to other point of consumption.

If desired the coal-like quality of the end reaction product may be altered, either by incorporating withl the complex residuum any suitable modifying agent, or by subjecting same .to further processing, while still in the low pressure vapor separator 47; provided such added agent and/or additional processing does Inot materially affect the quantity or quality of recycle vapor produced.

Where such treatment modies the fluidity of the residual complex in separator 47, so that same can no longer be pumped therefrom, a screw conveyor, or other known suitable means for its removal may be employed; or such and/or other modifying treatment may be applied'to the residual complex after withdrawal from the system, prior to its solidification into the previously described coal-like structure.

Primar charging of the system is effected by the ontinuously operated centrifugal pump 60, preferably drivenby electric motor 60' with automatic control and turbine stand- .by, taking suction on the hydrocarbon to be processed from an initial source of supply not shown in the drawing, through suction line 61; and discharging through line 61', heat exchanger 62, line 63, heat exchan er 64, line 65, heat exchanger 66 and line 6 blending supply tank 22Mwith control of iiow thereto effected by balanced valve 68 and float mechanism 68'; the arrangement of exchangers being in progressive andy counter current flow to the path of hot vapors, (principally of re-l cycle stock) so as to preheat the primary charging stock to a maximum degree within the limits of practical economic conservation of heat, and secure partial condensation of the recycle stock vapors in the previously enumerated exchangers. f

In this connection, as an aid to securing such economic conservation, all instrumentalities therein involved, in the previously mentioned and subsequently to be described process; including the still proper; 'low pires-l dephlegmating towers,

sure vaporizers, blending supply tank, heat exchangers, and the connecting lines thereto are to be considered as' adequately insulated, though not specifically sorshownin the accompanying drawing.

The initially produced recycle vapors from the low pressure vapor` separator 29, escape therefrom through vapor line 30, to valve nest 69, 69' and 69", controlling the iiow or by-passing of the hot vapors to exchanger 70, located 1n base of dephlegmating tower 71. The hot vapors and/or condensate of recycle stock, then pass through exchanger shell 64'; preheating the primary charging stock' passing through exchanger 64, and the flow through line 72, past stop valve 72' to secondary dephlegmating tower 73, the therein condensed recycle stock iowing by line 74, as controlled by balanced valve 75 and float mechanism 75 to blending supply tank 22. The latter tank is in turn connected to tower 73, through vapor line 76, permitting any light vapors generated in tank 22, to enter the upper portion of tower 7 3; the lighter gasoline fractions from such tower escaping through line 77, to exchanger shell 62', initially heating the primary charging stock introduced to the system through line 61', and thence passing through condenser' coil 78, maintained in condenser box 78', to receiving tank 79, from whence the condensed gasoline may be removed from the system or further refined therein or without as desired; or a portion of same may be continuously recycled to the top of tower 73 for dephlegmating control.

The crude gasoline vapors from the reflux tower 20, enter the dephlegmating tower 71 through lines 80 and 81 under a reduced pressure, as controlled by valve nest 82, 82', 82" and/or 83' for remote regulation; the preferred de-phlegmated fractions escaping from tower 71, through line 84, to condensing coil 85, located in condenser box 85', and thence y to receiving tank 86; from which the condensed gasoline. therein obtained may be removed from the system or further refined as desired.

The heavier condensed gasoline fractions dephlegmated in tower 71, with liquid level therein maintained by balanced valve 87, and float mechanism 87', escape through line 88, to condenser section 89, located in condenser box 89', and thence flow to receiving tank 90, from whence the condensate may be revmoved from system or further refined therein or without as desired. r

v -arious automatic thermometric and pressure controls, as well as recording thermometers and pressure gauges,.and indicating devices of like type, not indicated in the accomtions, the quantities of materials, concrete operating conditions, etc., incident tothe transformation of a 19 A. P. I. gravity, somewhat degraded midcontinent stock, as discharged.

from a pressure Ystill of the type explained,

will now be disclosed; 'the objectives beingY the formation of only gasoline (through in termediately\produced y'recycle stock), and

the previously described coal-like complex.

The 19 A. P. I. gravity stock, produced at the rate of, say 5 tons per hou/r, as 21.60% continuous reject fromthe still, with 200 lbs. of the 5 tons representing a complex of free Lcarbon, asphaltic bodies of high molecular weight andA other decomposition products of cracking, adsorbed in previously introduced,

finely divided hydrate of liine; is continuously discharged from the front transverse drum of the still at 770 F., under 130 lbs. pressure f X c e into the primary low pressure vaporizer,

where 4 tons per hour of 26A. P. I. gravit-y recycle stock are vaporized, to be later itself converted into gasoline and additional degraded stook; the balance of the material entering the low pre/ssure vaporizer, being discharged therefrom as a-secondary residuum of approximately 8 A. P. `I. gravity at 650 F.

The one ton of secondary residuum from the preceding treatment, is now heated in a coil of several thousand feet of pipe, at a speed of circulation sufficient to avoid *substantial cracking, and is discharged from such coil under a pressure of approximately 100 lbs., and at a temperature of about 875 F. into the secondary low pressure vaporizer; wherein the pressure is reduced to atmospheric, with accompanying vaporization of roughly 75 of the stock introduced, or for the quantities handled, 1% ton of heavy recycle vapor per hour, which in turnl is subsequently itself cracked into gasoline and additional degraded stock. The balance of the secondary residuum, amounting to l@ ton, and containing all of the original adsorbed lime complex, or` its resultantk solid decomposition products, is .continuously released from such vaporizer inl liquidform into any desirable receptacle, as for nstance, gondola cars; where it shortly assumes the dry, glassy, coal-like complex structure previously described.l

As'a *variation of these conditions, the secondary residuuni may be heated to `say 750 F., .anddischa'rgedunder a coilpressure of 75 lbs. into the seeondary louT pressure vaporizer, maintained under a vacuum `ofy 120 millimeters, obtainingl substantially the same final resultant vapori'zation aspreviously recounted; the coal-'like complex produced in eithercase being for example of the following composition- Per cent Volatile matter I v t 45.0 Fixed carbon v 50.0 i CaO (lime) 4.5 Other impurities 0.5

It will be understood the process is, however, not limited to the exact materlals, quantities, ratios, temperatures, and pressures disclosed in the preceding paragraph, nor to any specic adsorptive binder. N either 1s the process restricted to any partlcular apparatus or instrumentality that has been mentioned as incidental in securing the desired objectives, and what I claim is new and desire to protect'by Letters Patent 1s:-

1. AV processfor .producing a dry and 'frangible coal-like substance which includes by its contained heat suflicient of the remaining volatile liquid constituents as to leave a iuid residual product which solidifies at atmospheric temperatures to form the aforesaid coal-like substance.

2. A process for producing a dry and frangible coal-like substance which includes the steps of withdrawing an intimate mixture of degraded liquid petroleum hydrocarbons with an adsorptive binder of ashforming content from a body of hydrocarbon oils undergoing cracking; ashing and conducting off a portion of the volatile constituents of said mixture; condensing and returning a portion of said volatile constituents for further cracking to the body of hydrocarbon loils undergoing `cracking from which said degraded petroleum hydrocarbons are withdrawn; heating the residue of said mixture under pressure fora time inhibitive yof substantial cracking; andlinall releasing the pressure on said residue to suc an extent' as to vaporizebyits'contained heat suilicient of theremaining volatile liquid constituents as toA leave a fluid residual Y product which solidifies at atmospheric temperatures to form the aforesaid coal-like substance. l

3. A process for producing a dry and frangible coal-like substance which includes the steps of withdrawing an intimate mixture of degraded petroleum hydrocarbons with anash-forming content from a body of hydro-v carbon oils undergoing cracking;'flashing and conducting off a portion .of the volatile constituents of vsaid mixture; heating the residue of said mixture under pressure Ifor a. time inhibitive of substantial cracking; releasing the pressure on said residue to such yan extent as to vaporize by its contained heat suicient of the remaining volatile liquid constituents as to leave a luld residual product which solidifies at atmospheric temperatures to form the aforesaid coal-like frangible coal-like substance, which includes drawn; and finally releasing the pressure on the steps of continuously permitting vapors to escape from a body of hydrocarbon oils undergoing cracking; continuously returning non-gasoline fractions of said vapors to said body of hydrocarbons undergoing cracking; withdrawing an intimate vmixture of degraded petroleum hydrocarbons with an adsorptive binder of ash-forming content from said body of hydrocarbon oils undergoing cracking; flashing and conducting off a portion cf the volatile constituents of said mixture; heating the residue of said mixture under pressure for a time inhibitive of substantial cracking; releasing the pressure on said residue` to such an extent as to vaporize by its contained heat sufficient of the volatile liquid constituents as, to leave a luid residual product which solidities at atmospheric temperatures to form the aforesaid coal-like substance; and condensing and returning to said body of hydrocarbon'oils undergoing cracking portions" of the volatile constituents flashed from said withdrawn degraded hydrocarbons together with a quantity of linely divided lime and fresh petroleum hydrocarbon oils to be cracked.

5. A process Vfor'producing a dry and frangible coal-like substance which includes the steps of continuously permitting vapors .to escape from a body of hydrocarbon oils un- `dergoing cracking; continuously returning non-gasoline fractions of said vapors to said body of hydrocarbon oils undergoing cracking; withdrawing an intimate mixture of degraded petroleum with an adsorptive binder of ash-forming content from said body of hydrocarbon oils undergoing cracking; Hashing and conducting oif a portion of the volatile constituents of said mixture; heating the residue to such an extent as to vaporize by its contained heat suliicient of the volatile liquid constituents as to leave a fluid residual product which solidifies at atmospheric temperatures to form the aforesaid ,coal-like. substance; and passing in heat .in-

terchange with vapors flashed from the withdrawn degraded hydrocarbons fresh oil to be charged during said process into said body of hydrocarbon oils undergoing cracking.

6. A process for producing a dry and l frangible coal-like substance which includes the steps of withdrawing an intimate mixture of degraded petroleum hydrocarbons with an adsorptive binder of'ash-forming content 4from a body of hydrocarbon oils undergoing cracking; flashing and conducting ofl1 a portion of the volatile constituents yof said mixture.; heating for a time inhibitive of substantial cracking. the residue of said mixture under pressure in excess of the initial boiling point of the body of hydrocarbon oils undergoing cracking from which the liquid petroleumv hydrocarbons are with- Mfluid residue is obtained which forms a said residue to such an extent as to vaporize by its contained heat sufficient of the volatile liquid constituents as to leave a iiuid residual product which solidiiies at atmospheric temperatures to form the aforesaid coal-like substance.

7. In an oil cracking process wherein oil containing an adsorptive material, such as hydrated lime, associated with carbon reaction products formed in the cracking process is withdrawn from the oil undergoing cracking and conducted to a iiashing chamber where pressure is reduced and vapors removed, leaving unvaporized oil containing said adsorptive material associated with carbon reaction products, the steps of withdrawing and heating said unvaporized oil under pressure for a time inhibitive of substantial cracking whereby a permanent suspension in said oil`of said adsorptive matetial and associated carbon reaction products is obtained, subsequently reducing pressure on the unvaporized oil so heated and removing further "vapors therefrom whereb a r a solid fuel product of uniform compositidii upon cooling to atmospheric temperature without separation from the oil of the adsorptive material and associated carbon reaction products.

8. In an oil cracking process wherein oil containing an adsorptive material, such as hydrated lime, associated with carbon reaction products formed in the cracking process is withdrawn froml the 'oil undergoing cracking and conducted to a flashing cham: ber where pressure is reduced and vapors removed leaving unvaporized oil containing said adsorptive material associated with carbon reaction products, the steps'ofnpassing and heating a stream of said unvaporized oil under pressure for a time inhibitive of substantialV cracking whereby a permanent suspension in said oil of said adsorptive material and associated carbon lreactionproducts is obtained, subsequently reducing pressure on the unvaporized oil so heated and removing further vapors therefrom whereby a fluid residue is obtained which forms a dry, solid fuel product of uniform composition upon cooling to atmospheric temperature without separation from the oil of the adsorptive material and associated carbon reaction products.

9. A process for roducing amdry and frangible coal-like substance which includes the steps of introducing into a body of hydrocarabon oils undergoing cracking anadsorptive material, such as hydrated lime, withdrawing from saidbody of oil undergoing cracking a portion of the oil contain- -ing said adsorptive material associated with withdrawn oil and removing vapors therefrom leaving unvaporized oil containing said adsorptive material associated with carbon reaction products, passing and heating said unvaporized oil under pressure for a time inhibitive of substantial cracking whereby a permanent suspension in said oil of said adsorptive material and associated i carbon reaction products is obtained, subsequent-ly reducing pressure on the unvaporized oil so heated and removing further vapors therefrom, the amount of adsorptive material initially introduced into said oils undergoing cracking and the extent of the successive vaporizations with removal of vapors from'said withdrawn oils being regulated in such degree as to leave a fluid residue which solidiies into a dry, fuel product at atmospheric temperature and contains such quantity of hydrated lime as is Within the limits of the ash content of natural coal.

In testimony whereof I have aiixed my Si gnature.

ULYSSES S. J EN KIN S. 

